Method and means for hydrogenating unsaturated compounds.



H.K.MO0RL METHOD AND MEANS FOR HYDROGENATING UNSATURATED,CO-MPOUNDS.

APPLICATION FILED OCT. 31. I914. I 1,184,480. Patvnred May 25, 1916,

3 SHEETSSHEET l.

COMPRESSOR Z4 /0 HYDROGENATOR g' zi 7 i on. SEPARATOR COOLER 8 c cl/DEHYDRATOR COM F RESSOR RES STANc HEATER E DIRECT HEATER COOLERCOMPRESSED COM PRESSOR I O IOOLBS DEHYDFIATOR GA SOM ETER fuo'fijises:@7606 762 02":

i'aghfi ifabre 2V 4 f? H. K. MOORE. METHOD AND MEANS FOR HYDROGENATINGUNSATURATED COMPOUNDS.

APPLICATION FILED OCT. 31. 19M. 1,1 84,480. Patented May23, 1916. 4

3 SHEETS-SHEEI 2.

H. K. MOORE. METHOD AND MEANS FOR HYDROGENATING UNSATURATED.COMPOUNDS.

APPLICATION FILED OCT. 31| I914- 1,184,480. Patented May 23, 1916.

3 SHEETSSHEET 3.

I 72g Ja /z law/0 M650 Leg/o HUGH KQMooaE; or BERLIN, NEW. rrAMrsinaE.

METHOD AND MEANS FOR HYDROGENATING UNsAruRA'rEn COMPOUNDS.

Application filed October 31, 1914. Serial No. 869,689.

and Means for Hydrogenating Uusaturated- Compounds, of which thefollowing is a specification. I

This, invention has relation to the hydro genation of oils or fats, orother like unsaturated compounds such as the esters or glycerids of thefatty acids, the fatty acids,

etc., and it has for its object to provide certain improvements, notonly in the process of hydrogenating unsaturated compounds, but also incertain of the instrumentalities which maybe conveniently used inconnection therewlth, so that the process may be carried on commerciallyin an economical manner and the product placed upon the market at areasonable cost of production.

In general, the process, in its more essential features, is set forth inmy application Serial No. 821,241,'filed February 26,

1914, to which reference may be had for a general description thereof.

According to the process outlined in the said application, unsaturatedcompound (which for convenience I hereinafter term oil) is atomized by ablast of hydrogen and is caused to pass through a layer of finelydivided catalytic material, preferably held upon a diaphragm which ispervious to the hydrogen and oil but impervious to the catalyzingmaterial, the result of which is that the oil is hydrogenated and theprodnot is removed without carrying with it any of the catalyticmaterial.

One of the objects of the present invention is to insure the purity ofthe resultant product by preventing any deposit of carbonaceous materialin the. diaphragm or catalyzer such as would tend to discolor theresultant product;

Another object of the invention is to provide for supplying the hydrogenat a predetermined temperature, free of water or other foreignsubstance, irrespective of whether the hydrogen be that which waspreviously used in excess in the hydrogenation of the compound, or inthe reduction of the catalyst, or whether itbe drawn from its originalsource of supply.

Still another object of the invention. is toprovide instrumentalitiesfor.v accomplish- Specification of Letters Patent.

Patented May as, 1916.

King these desirable results, and to provide certain improvements in theinstrumental- 1t1es themselves.

A further object of the invention is to provide a body of catalyzingmaterial of a finely divided nature in such form that it will not crackor contract and permit the oil and 'hvdrogen to pass through withoutcoming into intimate contact'withthe catalytic materlal,

The invention has further for its object to provide other improvementswhich are illustrated upon the accompanying drawings, described in thefollowing specification and pointed out in the appended claims. I Y

Referring to the accompanying drawings,-Figure- 1 represents 1n planview -diagrammatically instrumentalities which may be utilized incarrying out my improved process. Fig. 2 represents: partially insection what I may term the hydrogena tor; that is, the instrumentalityin which- -the saturation of the compound is effected.

Fig. 3 represents an enlarged more or less conventional view of asection of the layer of catalytic material and the diaphragm. Fig. 4represents in section a drier which is utilized in abstracting anymoisture that may be therein contained. Fig. 5 illustrates alongitudinal section through the heater which is utilized for supplyingto the hydrogenator the hydrogen which is employed in reducing thematerial to its active cata'-- lytic condition for use as a catalyzer.Fig. 6 represents a form of heater, which I find convenient for heatingthe hydrogen which is being re-used in the hydrogenation of the oil.Fig. 7 illustrates a longitudinal section .through a separator which isemployed forv abstracting from the hydrogen, which has passed throughthe hydrogenator, any entrained oil. Fig, 8 represents a transversesection therethrough. Fig. 9 represents a section through one of thecoolers which is employed for condensing moisture out of the hydrogen. j

Before proceeding to describe one way in which the process may becarried out-and the instrumentalities which I have illustrated as beingcapable of convenient employment in connection with the"'process, Idesire to have it understood that the invention is not limited to theparticular process or the particular steps which I shall describe, norto the employment of the parp is essential before the actual .ticularform of apparatus. Ihave not attempted to illustrate the exact relativesizes of the various instrumentalities or their exact locations incarrying out the process, since Fig. 1 of the drawings is in the natureof a diagrammatic view in which the parts are located on the sheet ofdrawings where they can be seen to the best advantage. In point ofactual practice, the various instrumentalities are located relativelyclose together and at different elevations so as to obviate thenecessity of using long conduits for the hydrogen and to secure acompact ness of arrangement. Y

Referring now to Fig. 1 for a general description of a way in which theprocess may be practised,10 indicates what I term for convenience ahydrogenator in which the oil or other compound is reduced by hydrogenin the presence of a catalyzer. 4 This apparatus will be describedsubsequently more in detail. The oil, or other compound,

which is admitted to this apparatus, is drawn from anysuitable sourceand issupplied therefrom by a conduit 11. The hydrogen which may beobtained in any suitable way, as for instance, by the electrolyticdecomposition of sodium chlorid and water, may be stored in a gasometer12, from which it is drawn as needed. The first step which hydrogenationof the oil, is the reduction of the material to be used as a catalyzer.This necessitates the supplying of the hydrogen at a relatively hightemperature and in a condition in which it is free from moisture, oiland other impurities. To this end, I locate between the hydrogenator andthe gasometer, which I may for convenience term the source of supply,means for depriving the hydrogen of any entrained or dissolved moistureor other impurities. 13 indicates such means, which I may term thedehydrator, and which is supplied with any suit able hygroscopicmaterial for absorbing the moisture. This is preferably located betweenthe hydrogenator 10 and the tank 14, into which the hydrogen is pumpedby a compressor 15 fromthe gasometer 12. Be-

tween the compressor and' the storage tank is preferably placed a coolerand condenser 16. In the storage tank 14, the hydrogen may be held at apressure of approximately 100 pounds to the squareinch. From thedehydrator the gas is supplied to the hydrogenator 10 by a conduit 17,connected to a pipe 18 which leads into the top of the hydrogenator.From the lower portion of the hydrogenator the hydrogen is led byconduits 19 and 20 to a cooler 21, and thence through a dehydrator 22 toa compressor 23, and thence to a heater 24 by which the hydrogen isheated to the desired temperature. From the latter, it is conducted by acon duit 251 to conduit 26 connected to that at variable speed motor,

18. This much of the apparatus is utilized for the'reduction of thenickel oxid or other material which is used as a catalyst. After thedesired quantityof hydrogen is admitted to the upper chamber of thehydrogenator and has passed through the catalyzing material, it isheated by the heater 24 to the desired temperature and circulated againthrough the layer of oxid at the necessary temperature for the reductionthereof. The reduction takes place at approximately a temperature of 570F.

the application to which reference has already been made, and as will besubsequently described, thereis in the hydrogenator preferably adiaphragm in which the catalytic material is contained, this diaphragmserving to divide the hydrogenator into two chambers, one above, and theother below the diaphragm. A suitable difference in pressure ismaintained in these two chambers so that the hydrogen will be forced athigh velocity through the catalytic material in the diaphragm into thelower chamber. The hydrogen, which is delivered from. the lowercompartment through the conduit 19, is, when the reduction of the oil isproceeding, delivered to a conduit 25 connected to that at 19. This gas,if desired, "is passed through a cooler 261 like that at 16, where it iscooled sufiiciently to condense the vapors and to permit the separationof the resulting entrained oil in an oil separator which is indicated at27. The gas, which is thus freed from the oil, is 'delivered to thedehydratoror drier 28 which removes any remaining moisture and anyentrained oil, if there be any. From the dehydrator or drier thehydrogen is pumped by a .compressor 29 (preferably driven by a notshown) through a heatenindicated as a whole at 30, and

thence it passesthrough a conduit 31 to the conduit 26 by which it isagain delivered to the hydrogenating apparatus.

For the atomization of the oil, it is necessary that it be sprayed intothe hydrogenating apparatus by gas under a higher pressure than thatwhich is in the upper compartment of the hydrogenator; and hence, forthis purpose, I utilize .a relatively small compressor 32 which as shownmay draw gas from the main outlet 25 through of the compressor might beconnected with the pipe 26 instead of the pipe to reduce the work of thecompressor 32.

These various instrumentalities, which I have referred to thus briefly,are more especially desirable foruse in connection with thehydrogenation of oil for edible purposes -where the discoloration of theproduct is highly objectionable. I shall now. proceed to describe indetail I the various instrumentalities to Which I have briefly referred,but in so-doing, as I have already pointed out, I desire it to beunderstood that the invention is not limited to the use of suchparticular instrumentali- I ties, although I find them to be desirablefor accomplishing the purposes for which apparatus.

they are utilized. I have not complicated. the drawings by showing allof the various valves and pipes and fittings that maybe used to controlthe flow of oil and hydrogen,

' but it-will be understood that they are used 1 wherever necessary.

I will first describe the hydrogenating This is indicated as a whole at10, and, as illustrated comprises a large shell or casing, acrosswhichisplaced a grid 40 consisting of a plate provided with numerousrows of perforations. The upper surface of the plate is preferablyprovided with intersecting V-shaped, grooves 41, the bottoms of whichcommunicate with the apertures 42. Thus the upper surface of the plateis provided .With a series of rows of projections 43 of pyramidal form.This grid is utilized for supporting the diaphragm, and upon it isplaced a sheet of heavy steel wire cloth'44 which is preferably rolledto' flatten the exposed surfaces of the wires. The rolling of the clothprior to its using stiifens it and securely interlocks the wirestogether. Upon the wire cloth 44 is placed a second cloth 45 formed ofmuch finer wire and with much smaller mesh. These three elements, towit, the perforated grid and the two layers of wire cloth, con' stitutea support for the diaphragm, and the construction and arrangement issuch that the diaphragm is supported at very closely adjacent pointswhere it comes in contact with the layer of fine wire cloth so as toprevent its yielding or breaking. Upon the cloth 45 is placed a sheet 46of asbestos paper or its equivalent which is pervious to oil andhydrogen but impervious to the catalytic material. This catalyticmaterial is in a finely divided state and may be formed from any of theusual metals such as palladium, platinum, nickel, etc. Assuming that thenickel is to be used as a catalyzer, the oxid in a finely dividedcondition may be thoroughly mixed with long or stringy asbestos fiber,and a layer thereof is placed upon the sheet 46, as indicated at 47. Asecond sheet 48 of asbestos may be then placed upon the layer and asecond layer of asbestos fiber and nickel oxid laid thereon as indicatedat 49. To hold the layers in place, there is located above them a. sheet50 of fine wire cloth. If desired, a sheet of asbestos, not shown,.maybe interposed between the top layer of catalytic material bars placed inthe lower portion of the casing, as indicated in dotted lines at 52, todivide the easing int two compartments.

I have stated that the layer of catalytic material contains in mixturetherewith long fibered asbestos. This is merely a mechani- .cal mixture,the asbestos being utilized to prevent the layer of catalytic materialfrom' cracking, very much as hair has been used inplaster for the samepurpose. Only a very small quantity of the fibered asbestos is necessaryfor this purpose. After the diaphragm is formed, with nickel oxid, forinstance, for providing the active material, the hydrogen at a hightemperature is passed therethrough to reduce it to its active condition.The hydrogenfrom the pipe 34 is delivered to the rotary pipe 54 whichextends down into the casing and which is driven by a worm wheel 55 andworm 56 supported upon a frame 57 The pipe 54 is provided with a nozzle58 for directing the blast of hydrogen against the oil which isdelivered from the nozzle'59, thev latter being connected to a pipe 60,to which is coupled the pipe 11 leading from the source of oil supply.The two nozzles 58 and 59 are in close proximity, so that, as the oilissues from the nozzle 59,, it is blown across a portion of .the uppersurface of the diaphragm. The finely divided oil and hydrogen passthrough the layer of catalytic material and the oil is saturated orreduced by the hydrogen. As the nozzles revolve, the spray is directedtoward successive portions of the a which there may be as many asdesired, these pipes being connected to the-pipe 19 in Fig. I. Saidpipes are arranged above the bottom of the casing below the diaphragmand are provided onthe under portions of their peripheries with numerousholes or perforations leading to the interior thereof for the entranceof the gas. For the'protection of.

the pipes from the hydrogenated product, aprons or shields 64, which aresubstantially U-shaped in cross-section, are placed upon the ipes asshown, so that the hydrogenated pro uct dripping down will not beentrained to any considerable extent in the outflowing gas. For thepurpose of maintaining the temperature within the casing at the properpoint, the casing may be encircled by a series of pipesv 65 connected tothe manifolds 66, 67, superheated or high pressure steam being suppliedto the former and conducted away from the latter by suitable conduits.These pipes, as well as the entire exterior of the casing, arecompletely covered by one or more layers of insulating material such asmagnesia or other suitable substance to prevent the loss of heat byradiation. The pressure of the atmosphere of hydrogen above thediaphragm is maintained at a point considerably higher than the pressureof the atmosphere below the diaphragm to insure the passage of thehydrogen through the diaphragm at a high velocity, and the hydrogenwhich is blown in through the nozzle 58 is at a still higher pressure inorder to form the atomized blast.

One of the difficulties that I have met with practically in theoperation of an apparatus of this character havinga diaphragm a of largearea has been due to the occasional cracking of the catalytic layer andalso due to the expansion of the casing which forms 'cracks'or spaces atthe outer edges of the diaphragm, through all of which cracks and spacesthe hydrogen escapes into the lower compartment, the'reby permittingsome of the oil to pass through without being reduced, and so reducingthe pressure above the diaphragm that the gas will pass therethrough inonly limited quantities. I have overcome this difliculty byincorporating with the layer of catalytic material longfibered asbestos,as hereinbefore explained, which I find revents the formation of cracks.The di 'culty, due to the expansion of the casing, has been overcome bythe provision of the ring 51 which clamps the margins of the portions ofthe diaphragm supported in such way as not to obstruct the flow of thegas and the hydrogenated product through it. I accomplish this by thegrooved and perforated grid which may be made of such thickness as towithstand the pressure, and by the use of one or morelayers of-wirecloth placed thereon. Practically I employ two layers, the lower one ofheavier wire cloth and the upper one of a finer mesh,

in order that the asbestos may not be forced into the meshes. I

Cooler and condenser-Any suitable apparatus for removing moisture fromthe gas, as during the reduction of the catalyst,

may be utilized, but I have shown in Fig. 9 an apparatus which I utilizeat either 16 or 261 in Fig. 1. This apparatus may consist of an ordinarycondenser. Water is admitted to the lower-chamber-70, and, passingthrough the tubes 71 into the upper chamber 72, is conducted away. Thegas is admitted to the space between the tubes by the pipe 73 and isconducted therefrom by the pipe 74. As the cooling medium, I may useordinary river water at seasonable temperature. In the case of thecooler at 16, in Fig. 1, the greater part of the moisture contained inthe gas is condensed and removed. In the case of the cooler 261,however, not only is a portion of the contained moisture (if there beany) removed, but also a large portion of the oil which is dissolved inthe gas is condensed and removed therefrom or put in the condition ofentrainment, so that it may-be subsequently oil, which has been placedin condition forentrainment, I employ an oil separator, and

tothis end I may use an apparatus such as shown in Figs. 7 and 8. Thisseparator consists of an elongated cylinder80 having heads 81, 81,secured on the ends thereof. Within the cylinder is placed a number ofdisks 82 which are strung upon a rod 83 and spaced apart by sleeves 84.These disks are provided with numerous perforations, the perforations ofeach disk being out ofalinement with the perforations of the two adjacent disks. Leading from the space between each pair of disks, there isa trapped outlet pipe 85 communicating with a manifold 86. The gas andits entrained oil is admitted at one end through the pipe 87, and thegas freed from the oil is admitted through a pipe 88 at the other end.

As the gas with the entrained oil passes at high velocity through theseparator, the oil comes in contact with the plates and forms globulesthereon which gradually run down and are carried away through the pipes85 to the manifold 86. I have shown this form of separator which I havefound to be satisfactory for the purpose, but any other suitable formmay be utilized in lieu thereof.

The cZehydratr.-It is of great importance, not only in the hydrogenationof the oil but also in the reduction of the catalytic material,completely to remove, so far as possible, all moisture from thehydrogen, for, if the moisture remains in the gas, it will be broken upin the heater and the free oxygen and other oxygen compounds will injurethe catalyzing material. Consequently I employ what I term a dehydrator,such as shown in Fig. 4c. This may consist of a closed casing 90provided with staggered shelves 91, upon which is placed a quantity ofdehydrating or hygroscopic material such as fused calcium chlorid or thelike. The gas is admitted to the lower portion of the casing through apipe 92, and followinga tortuous path upwardly passes over and 'incontact with the dehydrating material and is finally emitted from thepipe 93. I preferably form the shelves 91 with numerous small aperturesthrough which the gas may pass upwardly through the layers ofdehydrating material thereon, and

preferably employ fused calcium chlorid for the reason that it has anafiinity for oil as well as for water, and, if any oil escapes from theseparator, it is taken up and removed in the dehydrator.

The heatera-In the reduction of the catalytic material, it is necessarythat the gas should be heated to' a relatively high heat; Whereas, forthe reduction of the oil, the gas need not be heated to such a hightemperatur although the temperature will be regulat (1 according to theproduct to be ohtained, say from 175 F. to 480 F., as I have alreadyexplained; and I therefore preferably employ two forms of heater, eachespecially designed for its particular purpose. In raising the gas toits highest temperature for the reduction of thecatalyzer, whichoperation takes but a relatively short time, say from 3 to 6 hours, andin which there is little or no possibility of oil having been entrainedwith the gas due to the gas having been drawn from its original sourceof supply, I find it possible to use the heat generated by electricallyresistant materials with which the gas may come directly in contact,thus enablingthe gas to be quickly raised to any desired hightemperature. It is necessary that such resistant materials be employedas will not be acted on by the hydrogen at the high temperatures towhich amperage and low voltage is passed through them coincidently withthe passage of the hydrogen through the interstices of the mass. In Fig.5 of the drawing, I have illustrated a heater in which the mass ofcarbon rods.100 is confined within a tube 101 formed of fire clay,magnesia or equivalent material. Into each end of the tube there isinserted a block 102 of Atcheson graphite, the periphery of which isgrooved or slabbed off so as to permit the passage of gas thereby, whileholding the resistant material in place. The blocks 102 are held inplace by metallic holders 103, against which bear the ends of screws104. These screws are passed through cylinder heads 1'05 insulated frombut bolted to a cylinder 106. The cylinder and the heads may be formedof metal. The shell or casing thus formed is completely inclosed withina covering 107 of heat-insulating material. Between the tube 101 and thecylinder 106 is placed a mass 108 of heat resistant material, such aspowdered fire brick or the like, which is sintered together to form asolid mass after it is put in place. The gas to be heated is admittedthrough a pipe 109 into the space between the filler 108 and one of thecylinder heads, and is conducted from the heater by a pipe 251-leadingto the pipe 26. Connected to the heads 105 are terminals 111 ofconductors leading from a secondary coil of a transformer indicated at113 in Fig. 1. A transformer of suitable character is employed for thepurpose of delivering a current of high amperage and low voltage; forinstance, a current of 2400 amperes at a maximum potential ofapproximately to volts. The current, I in passing from one of the blocks102 to the other through the mass of resistant material, heats thelatter at their multitudinous points of impingement to a hightemperature, so that the gas, in passing through the mass, is heated toa temperature necessary for the reduction of a catalytic material. I usea current of low voltage and high amperage in order to" prevent theformation of arcs such as would cause the hydrogen to react with thecarbon, with the formation of acetylene, while at the same time theresistant material is heated to a high temperature. The gas possesseslow powers of con ductivity, but, by being passed through theinterstices formed between the carbon rods which are packed together, isheated with but little loss of heat. It is possible to control thetemperature of the gas in either of two ways; first, by varying the flowof the gas through the heater, and, secondly, by increasing-ordecreasing the resistance in the circuit. The resistance may be variedby the adjustment of the screws 104. By packing the resistance materialmore closely together, a greater flow of current is permitted with aconsequent rise in temperature of the resistant material; whereas, bypartially unscrewing the screws so as to reduce the pressure of thepieces of resistant material upon each other, the resistance to thepassage of the current will be increased, and the heat generated will becorrespondingly diminished. This heater, as previously explained, ispreferably used only for raising the temperature of the gas which isutilized for the reduction of the catalyzing material, where there is nopossibility of oil passing through with the gas.

For heating the hydrogen, which has al ready been used in thehydrogenator, to a relatively lowertemperature which is necessary forthe reduction of'the oil, I may employ a heater such as shown in Fig. 6,in which case the gas is heated by conduction as it is passed through aseries of pipes by heating the pipes themselves. In Fig.

. 6, I have shown such a heater, which consists of a manifold 120 towhich the gas is supplied from the pipe 121. From the manifold 120 aseries of pipes 122 lead to a manifold 123 connected with the pipe 31,see Fig. 1. Around each pipe 121 there is one or more resistance coils124= inclosed within a layer 125 of insulating material. These pipes andthe manifold 123 are located within a casing 126 containing a packing ofnonconducting material 127. I may use for this purpose magnesium andasbestos fiber or any other equivalent substance. The resistance coilsare connected with the secondary of a transformer 128 so constructedasto provide a potential of 110 volts, which is the ordinary lightingcircuit. The gas, in passing through the pipes from one manifold to theother, is heated to the desired temperature. Any suitable form ofregulating device for the resistance coils may be utilized to regulatethe temperature of the gas. It

I have found the heaters which I have described to be satisfactory, butit will be understood that other forms of heating apparatus for thehydrogen may be utilized in lieu thereof.

I have thus described in detail the various instrumentalities which Irecommend for carrying out my process in order that persons skilled inthe art may have the advantage of the knowledge I have gained in thehydrogenation 'of unsaturated compounds, and in order that users of theprocess may be guided in the selection or construction of apparatussuitable for the purpose.

In my previous application I have pointed out the desirability ofsecuring a fine division of the oil prior to its reduction by thehydrogen, and I- also explained a theory I have formed of the reactionthat takes place during the reduction of the unsaturated compound. Laterdevelopments have lead me to believe that thecatalytic'materialdoes notformthe simple hydrid which I suggested as an example in thespecification of my application. While these later developments haveserved to confirm my belief that unstable hydrids are formed, yet I amnow inclined to the opinion that these hydrids are more complex, such aswould be represented by the formula Ni OH where as may indicate avariation within considerable limits. Quite irrespective of my theory,however, it is unquestionably the fact that, by my process, unsaturatedcompounds may be commercially reduced by a continuous process and to thedesired point of saturation, and the catalyzer may be revivified whenthe same becomes sluggish or inactive by passing the hydrogentherethrough.

So far as my work has gone, I have been unable to determine the limitsof indestructibility of a given quantity of the catalyzer, whenrevivified from time to time as directed in my earlier application.\Vhile the asbestos layers of the diaphragm occasionally requirerenewal, due" to their being plugged by albuminous matter, yet I havediscovered no deterioration of the catalytic material itself. In thisconnection I may refer to the fact that I have herein suggested theemployment of a compressor driven at vairable speeds, so that, as theasbestos portion of the diaphragm gradu ally becomes increasinglyresistant to the passage of the hydrogen and the reduced producttherethrough (on account of the accumulation of albuminoids or othersubstances), the pressure and volume or weight be correspondinglyvaried. In explanation,

there is a physical and chemical law whichmay be statedroughly asfollows :-In a gaseous reaction tending to reduce the'number ofmoleculespresent, the reaction is directly proportional to the pressure. In thepresent case, notwithstanding the oil or other compound may be a liquid,I believe the reaction to be gaseous, in view of the fine atomization ofthe compound. Hence, in the hydrogenation, I maintain the hydrogen underhigh pressure. As the diaphragm clogs, which would naturally cause agradual increase in the pressure above the diaphragm (assuming thedelivery of the hydro-gen from the compressor to be at a constantpressure and volume), it is desir- I consists in circulating hydrogen inexcess into contact with oil through a diaphragm containing a catalyzerto reduce the oil, and

cooling the unused excess hydrogen for the condensation and removal ofcontained vapor.

2. The herein described process which consists in circulating hydrogenin excess into contact with oil through a-catalyzer contained in adiaphragm pervious to the oil and gas but impervious to the'catalyzer toreduce the oil, condensing the vapors contained in the excess unusedhydrogen, and separating from such hydrogen the entrained moisture andoil.

3. The herein described process of hydrogenating oil which consists inpassing hydrogen and oil under pressure through a catalytic diaphragmpervious to oil and hydrogen and impervious to the catalytic material,and decreasing the weight ofthe hydrogen being fed as the resistance tothe passage of the hydrogen therethrough increases, so as to preserve auniformity of pressure on the diaphragm.

4. The herein described process which consists in circulating hydrogenin excess into contact with oil and a catalyst to reduce the oil,condensing and removing moisture and entrained oil from the unusedexcess hydrogen, heating said hydrogen, and reusing such hydrogen forthe reduction of more 5.- The herein described process which consists incirculating hydrogen in excess into contact with oil and a catalyst toreduce the oil, cooling the unused hydrogen to condense vapors, removingmoisture and entrained oil from such cooled hydrogen, then heating thehydrogen and then reusing the same for the reduction of more oil.

6. The herein described process which consists in circulating a volumeof hydrogen through a mass of catalytic material, atomizing a stream ofoil by a separate stream of hydrogen and passing the atomized oilthrough the catalytic material.

7. The herein described process which consists in atomizing a stream ofoil by a stream of hydrogen on one side of a pervious diaphragmcontaining a catalyzer, supplying an additional stream of hydrogen onthe same side of said diaphragm, and passing-the atomized oil and excesshydrogen through said diaphragm into contact with said catalyzer, andwithdrawing the hydrogenated product.

8. The combinationv with a hydrogenatlng apparatus, and a supporttherein for a body of catalytic material, of means for circulating gasthrough said apparatus and catalytic body for the reduction of thecatalyst, including a cooler for condensingthe contained moistur in thegas, means for dehydrating said gas, 'a compressor, and a heater for thegas.

9. The combination of a hydrogenating chamber, means therein forsupporting a layer of catalytic material, means for purifying, heatingand circulating gas through said hydrogenating chamber and catalyticmaterial to reduce such material, and-separate means for purifying,heating and circulating gas in excess through said chamber and catalyticmaterial for the hydrogenation of an unsaturated compound.

10. The combination with a hydrogenating apparatus comprising anatomizer for hydrogen and oil, and an independent inlet for hydrogen, ofmeans including a pump for forcing hydrogen discharged from saidapparatus through said atomizer, and means connected with said inlet forcirculating hydrogen through said apparatus, including a pump, means fordepriving the hydrogen of contained vapor and oil, and a heater for thehydrogen.

11. The combination with a hydrogenating apparatus of means for'circulating excess' hydrogen therethrough comprising a condenser, anoil separator, a dehydrator, a compressor, a heater, and conduitsconnecting the same so that the hydrogen passes through the same in theorder named.

12. The combination with a hydrogenating apparatus having oil andhydrogen nozzles for atomizing the oil, of a compressorfor forcinghydrogen through its appropriate nozzle, and a compressor for forcinghydrogen in excess into said hydrogenator.

13. The combination with a casing having a layer of catalyzing materialtherein, and nozzles therein for atomizi ng oil by a blast of hydrogen,of a compressor for delivering hydrogen under high pressure to theatomizer-nozzle, and a compressor for delivering excess hydrogen underlower pressure to said casing.

14:. A diaphragm for oil-hydrogenating apparatus, comprising a layer ofmaterial impervious to a finely divided solid but pervious to hydrogenand oil, and a layer thereon consisting of a catalyst capable ofreducing oil with hydrogen and having mechanically mixed therewith orincorporated therein a fibrous material for preventing the formation ofcracks.

15. The combination with a casing, of a grid therein, said grid beingprovided with apertures, and with intervening projections on its uppersurface, a layer of coarse wire cloth resting on said projections, asuperposed layer of fine wire cloth, and a catalytic diaphragm restingthereon.

16. The combination of a casing, a diaphragm therein provided withcatalytic materiahmeans for supplying oil and gas to the interior of thecasing above the dia phragm, an outlet below the diaphragm for thehydrogenized product, and a transverse eduction pipe for the hydrogenbelow the diaphragm, having openings in its under portion.

17. The combination of a casing, a diaphragm therein provided withcatalytic material, means for supplying oil and gas to 19. Thecombination with an apparatus for the hydrogenation of .oil, of 'aheater, a. dehydrator having hydroscopic material, and means for forcinghydrogen first through said dehydrator and then through saidvheater tosaid apparatus.

In testimony whereof I have afiixed my signature, in presence of twowitnesses.

HUGH K. MOORE. Witnesses:

MARCUS B. MAY, P. W. PEZZETTI.

